Monoazo dyestuff pigments



United States Patent 3,366,623 MONOAZO DYESTUFF PIGMENTS Karl Ronco, Riehen, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed Mar. 15, 1965, Ser. No. 439,937 Claims priority, application Switzerland, Mar. 20, 1964, 3,621/ 64 6 Claims. (Cl. 260-203) ABSTRACT OF THE DISCLOSURE Monoazo dyestufi pigments of the formula The present invention provides monoazo dyestuff pigments of the formula =NR1Y-NIIR4 OH Rf CONHRs I in which R represents a benzene radical containing a nitro group in ortho-position to the azo group, R represents a naphthalene radical in which the azo, hydroxy and carboxylic acid amide groups are in 1, 2, 3-position, R represents a benzene radical, R and R represent aryl radicals, for example, naphthalene radicals, but especially benzene radicals, X represents a carboxylic acid or sulfonic acid amide group, Y represents a CO or an SO group and Z represents a hydrogen atom or a group of the formula X--R Since the dyestufis of the invention are to be in the form of pigments, they must not contain groups imparting solubility in water, especially acidic groups imparting solubility in water, for example, sulfonic acid or carboxylic acid groups.

The new dyestuffs may be obtained when (a) an azo dyestulf monocarboxylic acid halide free from acidic groups imparting solubility in water and corresponding to the formula in which R,, R and Y have the meanings given above and R represents a naphthalene radical in which the azo, hydroxy and carboxylic acid halide groups. are in l, 2, 3-position, is condensed with a monoamine free from 3,366,623 Patented Jan. 30, 1968 2 acidic groups imparting solubility in water and corresponding to the formula HaN-R in which R R X and Z have the meanings given above, or (b) an azo dyestuff monocarboxylic acid halide free from acidic groups imparting solubility in water and corresponding to the formula N =N Rl C OHal is condensed with an arylamine free from acidic groups imparting solubility in water, especially an aminobenzene, or (c) an azo dyestufi dicarboxylic acid halide free from acidic groups imparting solubility in water and. corresponding to the formula N=NR1COIIal is condensed in a molar ratio of 1:2 with an arylamine, or (d) a diazo compound of an amine of the formula (6) H NR Y-NH-R is coupled with a naphthol of the formula (7) on Rf z CONHR.a

, Iii-R or (e) a diazo compound of an amine of the formula (8) H N--R -Y-NHR is coupled with a naphthol of the formula (9) CHzA.

OH R z CONH-Ra in which A represents the radical of an amine and R R R X and Z have the meanings given above.

In method (a) of the process of the invention the starting materials used are advantageously azo dyestufl carboxylic acid chlorides of the formula in which X X and X represent hydrogen or halogen atoms or alkyl, alkoxy, trifluoromethyl, cyano or carbalkoxy groups and Z represents a hydrogen or halogen atom or an alkoxy group.

The corresponding azo dyestuff carboxylic acids are obtainable by coupling a diazo compound of an amine of the formula (11) OzN Xi HzN-OOONH :2

X3 in which X X and X have the meanings given above, with a 2:3-hydroxynaphthoic acid of the formula 3- or 4-chloraniline,

2: Sdichloraniline,

2 z 4: S-trichloraniline, 4-bromaniline,

2-, 3- or 4-methylaniline,

2: 5- or 2 6-dimethylaniline, 2-chloro-S-methylaniline,

2: 3- or 4-methoxyaniline, Z-methoxy-S-rnethylaniline, 2:4-dimethyl-S-chloraniline, Z-methoxy-S-ch1oraniline,

2 5 limethoxy-4-chloraniline, 2-methoxy-5-methyl-4-chloraniline, 3-trifluoromethylaniline,

3 :5-bis-trifiuoromethylaniline, 2-chloro-5-trifluoromethylaniline, 4-cyanoaniline,

3. or 4-carbomethoxyaniline, 2-chloro-5-carbomethoxyaniline, 2: S-bis-carbomethoxyaniline, 4-chloro-2 S-dimethoxyaniline, 5-chloro-2:4'dimethoxyaniline, 2-methoxy-S-trifluoromethylaniline, 4-acetylamino-3-trifluoromethylaniline or 2 S-dimethylaniline and then splitting off the formyl group in the condensation product obtained.

Conversion of the azo dyestuff carboxylic acids into their acid halides, for example, chlorides or bromides, is carried out, for example, with phosphorus halides, for example, phosphorus trichloride, phosphorus pentachloride or phosphorus pentabromide, phosphorus oxychloride or preferably with thionyl chloride.

The treatment with acid halogenating agents of the kind defined is advantageously carried out in an inert organic solvent, for example, dimethylf ormamide, a chlorobenzene, for example, monochlorobenzene or dichlorobenzene, toluene, xylene or nitrobenzene, if necessary, with the addition of dimethylformamide when using the last five solvents named.

When preparing the carboxylic acid halides it is generally advantageous to dry the azo compound if it has been prepared in aqueous medium, or to free it from Water by azeotropic distillation in an organic solvent. If desired, said azeotropic drying may be effected immediately before the treatment with the acid halogenating agent.

The azo dyestuif carboxylic acid chlorides so obtained are condensed with monoamines of the Formula 3, especially with those of the formulae in which formulae X has the meaning given above, Y represents a hydrogen or a halogen atom or an alkyl group, Y represents a hydrogen or halogen atom or an alkyl or alkoxy group, Y represents a hydrogen or halogen atom or an alkyl, alkoxy or aliphatic acylamino group, Y represents a hydrogen or halogen atom or an alkoxy group, Z and Z represent hydrogen or halogen atoms or alkyl, alkoxy, phenyl, carbalkoxy, cyano or aliphatic acylamino groups, Z and Z represent hydrogen or halogen atoms or alkyl, alkoxy, nitro tritiuoromethyl, cyano, carboxylic acid amide or carboxylic acid ester groups and Z represents a hydrogen or halogen atom or an alkyl, alkoxy, carboxylic acid amide, carboxylic acid ester or benzoylamino group.

As examples of amines of the Formula 13 there may be mentioned:

4-benzoylarnino-aniline,

2: 5-dichloro-4-benzoylamino-aniline,

2: 5-dichloro-4-(4-chlorobenzoylamino) -aniline,

2 5-dichlor'o-4- 2 :4'-dichlorobenzoylamino) -aniline,

5-dichloro-4- 2' 5 Riichlorobenzoylamino -aniline,

5 dichloro-4- 4-methylbenzoylamino) -anilinc,

-dichloro-4- (4'-phenylbenzoylamino) -aniline,

-dimethyl-4-benzoylamino-aniline,

-dimethyl-4- (4'-chlorobenzoyla-mino) -aniline,

-dimethyl-4- (2 4'-dichlo robenzoylamino -aniline,

-dimethyl-4- (2'-5 -dichlorobenzoylamino) -aniline,

5 -dimethyl-4- (4'-methylbenzoylamino -aniline,

2: 5-dimethyl-4-(4'-phenylbenzoylamino) -aniline,

2: 5-dimethyl-4-(4-methoxybenzoylamino)-aniline,

Z-chloro-S-methyl-4-benzoylamino-aniline,

2-chloro-5-methyl-4- (4-chlorobenzoylamino -aniline,

2-chloro-5-methyl-4- (2 5 '-dichlorobenzoylamino aniline,

2-chloro-5-methyl-4- (4-methylbenzoylamino -aniline,

2-chloro-5-methyl-4- (4'-phenylbenzoylamino -aniline,

2-methoxy-5-chloro-4- (benzoylamino -aniline,

2-methoXy-5-chloro-4- (4-chloro'benzoylamino aniline,

2-methoxy-5-chloro-4- (2 5-dichlorobenzoylamino) aniline,

2-methoxy-5-chloro-4- 4-methylbenzoylamino -ani1ine,

2-methoxy-5-chloro-4- 4'-phenylbenzoylamino -anilinc,

4- (4-carbomethoxy -benz oylamino-aniline,

2 5-dichloro-4-(4'-carbethoxy) -benzoylamino-aniline, and

2 5 -dimethy1-4- (4'-carbomethoxy) -benzoylarnino-aniline,

As examples of amines of the Formula 14 there be mentioned:

4-chloro-3 -aminobenzoic acid- 2' 5'-dichloro) -anilide,

4-methoxy-3-aminobenzoic acid- (2 5'-dichloro) -anilide,

4-chloro-3-aminobenzoic acid-(3'-trifiuoromethyl)-anilide, 5

4-chloro-3 -aminobenzoic acid- 2 5 '-dimethyl-4'-chloro) anilide,

5-amino-2:4-dichlorobenzoic acid-(3'-trifluoromethyl)- anilide,

4-chloro-3-aminobenzoic acid-(5'-trifluoromethyl-2'- chloro) -anilide,

4-methoxy-3-aminobenzoic acid-(5-trifluoromethyl-2'- chloro) -anilide,

4-chloro-3-aminobenzoic acid-(5'-carbomethoxy-2'- chloro -anilide,

4-methoxy-3-aminobenzoic acid-(5: 8-dichloro-u,-

naphthyl) -a-mide,

4-methoxy-3-aminobenzoic acid-(5'-carbomethoxy-",-chloro -anilide,

4-chloro-3 -aminobenzic acid-(2' '-dimethyl-4'-chloro anilide,

4-chloro-3 -aminobenzoic acid- (3 5 '-ditrifluoromethyl) anilide,

1-benzoylamino-4-(3-amino)-benzoylaminobenzene,

1-benzoylamino-4-(4'-chloro-3-amino)-benzoylaminobenzene, and

1 :4-dichloro-2-benzoylamino-5- (4'-chloro-3'-amino) benzoylaminobenzene. As examples of amines of the Formula there may 'be mentioned:

1-amino-2 S-dibenzoylaminobenzene,

1-amino-2: S-di- (parachlorobenzoylamino -benzene,

1-amino-2 5-di-( 2 4'-dichlorobenzoylamino) -benzene,

and

1-amino-2:S-di-(4-carbomethoxybenzoylamino)- benzene.

As examples of amines of the Formula 16 there may be mentioned: 1

may

aminoterephthalic acid dianilide, aminoterephthalic acid di-(para-chloranilide), aminoterephthalic acid-bls- (2' 5 -dichloranilide aminoterephthalic acid-di-(meta-trifluoromethylanilide), aminoterephthalic acid-dia-naphthylamide l-amino-benzene-3:S-dicarboxylic acid dianilide, 1-arnino-benzene-3 :S-dicarboxylic acid-di- (para-chloranilide), and aminoterephthalic acid-di- (para-methoxyanilide) In method (b) of the process of the invention the startingmaterials advantageously used are carboxylic acid halides of the formula in which Y Y Z Z and Z have the meaning given above. They are advantageously condensed with aminobenzenes of the formula in which X X and X have the meanings given above.

In method (0) of the process of the invention the starting materials advantageously used are dicarboxylic acid halides of. the formula in which Z Y and Y have the meanings given above.

They are advantageously condensed with aminobenzenes of the Formula 18 in a molar ratio of 1:2. v

Condensation between the carboxylic acid halides of the kind defined above and the amines is advantageously carried out in an anhydrous medium. Under such conditions it generally proceeds surprisingly quickly at the boiling temperatures of the common organic solvents, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. In order to accelerate the reaction it is generally advantageous to add an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the dyestuffs so obtained are crystalline and some are amorphous, and

they are generally obtained in a very good yield and in a pure state. It is advantageous first to isolate the acid chlorides which have been obtained from the carboxylic acids. In some cases, however, isolation of the acid chlorides can be omitted without harm, and condensation carried out immediately after the formation of the carboxylic acid chlorides.

In method (d) of the process of the invention for the production of the new dyestufls, a diazo compound of an amine of the Formula 6, especially one of the Formula 11, may be coupled with a naphthol of the Formula 7. v

Coupling is advantageously carried out in a manner such that a acidic solution of the diazonium salt is coupled continuously with an alkaline solution of the coupling component in a mixing nozzle, coupling taking place immediately. Care must be taken toensure that the diazo component and coupling component are present in the mixing nozzle in equimolecular proportions. The simplest method of doing this is to control the pH value of the liquid in the mixing nozzle. It must also be ensured that the two solutions are violently agitated in the mixing nozzle. The dyestuff dispersion that is formed is drawn oil from the mixing nozzle continuously and the dyestutf isolated by filtration.

In method (e) of the process of the invention for the production of the new dyestuffs, a diazo compound of an amine of the'Formula 4 may be coupled with a naphthol of the Formula 9.

In the compounds of the Formula 9, A advantageously represents the radical of an amine of the formula in which R represents a hydrogen atom or an alkyl radical and R represents an alkyl radical, the radicals R and R also being capable of forming a heterocyclic ring together with the nitrogen atom. As examples there may be mentioned the radicals of methylamine, dimethylamine, diethylamine, diethanolamine, pyrrolidine, piperidine and morpholine. The compounds of the Formula 9 are obtainable by reacting the compounds of the Formula 7 With formaldehyde and a primary or secondary amine. During coupling, the radical -CH A is split off and replaced by the azo group. Coupling is advantageously carried out in an acid medium.

The new dyestuifs are valuable pigments that can be used for a very wide variety of purposes. For example, they can be used in a state of fine division for the spindyeing of filament and staple fibre viscose rayon, celluwhich precipitated in the form of irregular, needle-like crystals was isolated by filtration, washed with a small amount of cold ortho-dichlorobenzene and benzene and then dried in vacuo at 50 to 60 C. 9.5 parts of this lose ethers and esters, polyamides, polyurethanes and monoazo dyestulf monocarboxylic acid chloride in adpolyesters, as Well as in the preparation of colored lacmixture with 5.4 parts of 4-c hloro-3-aminobenzoic acrdquers and as lake formers. They can also be used for (3-trifluorornethyl)-anilide in 350 parts of ortho-dlchlocoloring solutions and products made from cellulose acerobenzene were heated for 12 hours at 140 to 145 C. tate, nitrocellulose, natural and synthetic resins, for exam- Subsequently, the sparingly soluble pigment that precipiple, polymerization and condensation resins, for example, tated in the form of thin, bent needles Was isolated from aminoplasts, alkyd resins, phenoplasts, polyolefines, for the hot reaction mixture by filtration, washed with hot example polystyrene, polyvinyl chloride, polyethylene, ortho-dichlorobenzene, methanol and hot water and then polypropylene, polyacrylonitrile, rubber, casein, silicones dried in vacuo at 70 to 80 C. The dyestufi so obtained, and silicone resins. They can also be used with advantage which corresponded to the formula in the manufacture of colored pencils, cosmetic prepara- OZN C1 tions and laminated sheet material. l The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight. L

Example 1 I -on 01 108 parts of a dyestuff obtained by drazotising 4-am1no- 1 3-nitrobcnzoic acid (2-chloro-5'-trifluoromethyl)-anilide with glacial acetic acid, hydrochloric acid and sodium 3 nitrite and coupling with 2:3-hydroxynaphthoic acid, was l GONH- m1xed with 3,500 parts of ortho-dlchlorobenzene, 4 parts of f g g fi i fi f gd z 6 3 i i was an orange pigment sparingly soluble to insoluble in 2 ea oursfa th W 16 i i the common solvents and colored polyvinyl chloride film .g g qg f 2 mlx me e mono'car Oxy is brilliant orange tints possessing an excellent fastness to am 0 on e o e Ormu a light and migration.

11702 The monoazo dyestutf monocarboxylic acids obtainable from the binuclear diazo components listed in column fi I and the coupling components listed in column II of the following table can be reacted in the manner described I a in the first and second paragraphs above via the monoazo dyestuff monocarboxylic acid chlorides with 1 mol of the aromatic monoamines listed in column 111. The (31 tints produced in polyvinyl chloride film with the pigments thus obtained are given in column IV.

I II III IV 1 -amino-S-nitrobenzoic acid-(2-chloro-5-tri- 2:3-hydroxynaphthoic acid.... 4-chl0ro-3aminobenzoic acid-(4"chloro)-anilide Orange.

fluoromethyl)-anilide. 2 d .d0 i-chloro-3-anunobenzoic acid-(2:5-dichloro)- Do,

8H 6. 3 do do 5-amino-2ztdichlorobenzoic acld-(2:5'- D0,

dichl0ro)-anilida. 4 d0 do 4-metlhgxy-3-aminobenzoic acid-(2':5-dich1oro)- Do.

8111 I 9. 5 d do 4-methoxy-3-aminobenzoic acid-(3-tritluoro- Do.

methylyanilide. 6 do .do 2-amin0-1 4-diacetylaminob enzene Do. 7 do do 5-flml150i)S0phth8-ll0 acid-di-(4-chloropl1enyl- Do,

BJIll 6 8 do Z-amino-l i-di- (4-chlor0b cnzoylamino) -b enzene D o, 9 .do 2 fi-dichloro- (4-chloro-3-a-mino) -b enzoyl- D0.

amino-l-benzoylaminobenzene. 10...- d0 do 2:odichloro--(4-meth0xy-3-amino)-benz0yl- Do.

amino-1-bcnzoylaminobenzene. 11.... do d0 2:S-dichloro--(4-chl0ro-3-amino)-benzoyl- Do.

amino-l-(4"-chl0r0)-benzoylaminobenzene. 12 .do ..do 2:5-dichloro-4-(5-amino-2':4-dichloro)-benzoyl- D amino-1-(4011101'0)-benzoylaminobenzene- 13.... 4-amino-3-nitrobenzoic acid-(3-trifiu0ro- .do 2z4:5-trichloro-(4-methoxy-3-amino)-benz0yl- Do.

methyD-anilide. aminobenzene. 14.... do ..do 3-tritluoromethyl-(4-methyl-3-amino)-benzoyl- D0.

aminobenzene. 15.... .do ..d0 3-trifiuoromethyl-(4-methylmercapto-3- Do.

amino)-benzoylaminobcnzene. 16.... -.do ..do 2:5-dichlor0-(4-methoxy-3-amino)-benzoyl- D0.

aminobenzene. 17.... .do ..do 2:5-dimethyl-4-chloro-(4'-chloro-3"amino)- D0.

benzoylaminobenzene. 18.... ..-..do ..do 2:fi'dichloro-(4-chloro3-amino)-benz0yl- D0.

aminobenzene. 19.... ..-.do ..d0 3-trifluoromethyl-(4-chlor0'3-amino)-benzoyl- D0,

aminobenzene. 20...- .....do ..do B-tn'fiuoromethyl-(4-methoxy-3-amino)- D0.

henzoylaminobenzene. 21.... .-...do ..d0 4-ch1oro-( i chloro-y-amino)-benzoy1amino- D0.

benzene. 22.... .....d0 ..d0 2:5-dichloro-(5'-amino-2:4-dichloro)-benzoyl- D0.

aminobenzene. 23...- .....do d0 2:5-dichlor0-4-(4-methoxy-3-amino)-benzoyl- D0.

amino-1-benzoylaminobenzene. 24 .do ..d0 Z-amino-l:4-diacetylaminobenzene D0. 25...- 4-amino-3-nitrobenzoic acid-(2:5-dichl0ro)- d0 5:S-dichloro-(4-methoxy-3-amino)-benzoyl- Red.

anilide. aminonaphthalene. 26.... .....do ..do Eltn'fluoromethyl-(5-amin0-4-methoxy-2- Orange.

chloro)-benzoylaminobenzene.

I II III IV 83 do do 3:5-ditrifiuoromethyl-(4-chloro-3-amino)- D0.

benzoylaminobenzeno. 84.". 4-arnino-3-nitrobenzoic acid-(4-n1eth0xy)- do 2:5-dichl0ro-(5-amin0 2:4-dichl0ro)- D0.

anilide. benzoylaminobenzene. 85 4-amino-3nitr0benzoic acid-(2:5-dimethoxydo 2:5-dichloro-(5-amino-2:4-dichlor0)- Red 4-chloro)-anilide. benzoylaminobenzene. brown. 86. 4 amino-3-nitrobenz0icacid-(5-cl1loro-2- .do 4-benz0ylamino-l-aminobenzene D0.

methoxy)-anilide. 87 do do 4-chloro-3-amin0benzoie acid anilide Orange. 88 do do. 2:5-dichloro-(5-amino-2:4-dichl0r0)- D0.

benzoylaminobenzene. 89 do d 4-methoxy-li-aminobenzoic acid anilirle Do. 90".. i-amino-ii-nitrobenzoic acid(3'- do 2,5-diehl0ro-4-(5 amino-2,4-dichl0ro)- Do.

trifiuoromethyl)-anilide. benzoylaminobenzene.

Example 2 13.5 parts of monoazo dyestuif obtained by diazotisiug I H In 4-arnino-3-nitrobenzoic acid with glacial acetic acid, hy- 1 4 3 4 hl d 3, 4 U

-amino- -c oro-3- y roxy- -cior0-3-amiuodrochloric acid and sodium nitrite and coupling wrth 4 nitmbm naphthoyuammm benzoic acid chloro-3-(2 -hydroxy-3 -naphthoyl) amrnobenzoic aCld- 2O zoie acid. bentzkpitlz acifildy-trifluoromethyl ester.

me y am e. 3 -tr1fiuoromethyl-amhde, was mixed with 200 parts of 2 do "do ortho-dichlorobenzene, 0.3 part of dimethylformarmde 3 d d mjgillylanlline. and 4.3 parts of thionyl chloride and heated for 3 hours g ig fgfifgg at 115 to 120 C. while stirring. After cooling the reaction 4 ..do do 3-trifliioromethylmixture, the monocarboxylic acid chloride of the formula 5 "do ,g f gig am me. N0 2:5-dicl1loraniline. 2:4:5-t1'ichloraniline.

N COCl 1% r Example 3 OH Cl which precipitated in the form of regular, needle-like crystals, was isolated by filtration, washed with a small amount of ortho-dichlorobenzene and benzene and then dried in vacuo at to C. 1.39 parts of this monoazo dycstuif monocarboxylic acid chloride were heated for 12 hours at 140 to 145 C. in 150 parts of ortho-dichlorobenzene in admixture with 0.5 part of 3:S-di-(trifiuoromethyl)-aniline. Subsequently, the crystalline, sparingly soluble pigment that precipitated was isolated from the hot reaction mixture by filtration, washed with hot ortho-dichlorobenzene, methanol and hot water and then dried in vacuo at to C. The dyestuif so obtained corresponding to the formula C Fa was an orange pigment sparingly soluble to insoluble in the common solvents and colored polyvinyl chloride film brilliant orange tints possessing an excellent fastness to light and migration.

The monoazo dyestuff monocarboxylic acids obtainable from the aminocarboxylic acid diazo component listed in column I of the following table and the coupling component listed in column 11 can be reacted in the manner described in the first paragraph above via the monoazo dyestuff monocarboxylic acid chloride with 1 mol of the aromatic monoamines listed in column III. The orange tints produced in polyvinyl chloride film with the pigments obtained displayed excellent properties of fastness.

22 parts of a monoazo dyestuff obtained by diazotising 4-amino-3-nitrobenzoic acid with glacial acetic acid, hydrochloric acid and sodium nitrite and coupling with 2- hydroxy-3-naphthoic acid-2'-chloro-5-carboxyanilide, was mixed with 200 parts of ortho-dichlorobenzene, 0.5 part of dimethyl formamide and 13 parts of thionyl chloride and heated for 2 hours at to C. while stirring. After the reaction mixture, the crystalline dicarboxylic acid chloride of the formula Ifil -COOl N l was isolated by filtration, washed with benezene and then dried in vacuo at 50 C. 16.4 parts of this monoazo dyestuif dicarboxylic acid chloride were heated for 12 hours at to C. in 700 parts of ortho-dichlorobenzene in admixture with 11 parts of 4-chloro-3-aminobenzoic acid methyl ester. The sparingly soluble pigment that precipitated was isolated from the hot reaction mixture by filtration, washed with hot ortho-dichlorobenzene, methanol and hot water and then dried in vacuo at 70 to 80 C. The dyestuff so obtained corresponding to the formula l COOCI-Ia 13 was an orange pigment sparingly soluble to insoluble in the common solvents. It colored polyvinyl chloride film brilliant orange tints possessing an excellent fastness to light and migration.

The monoazo dyestuff dicarboxylic acid obtainable from the diazo component listed in column I of the following table and the coupling component listed in column II can be reacted in the manner described in the first paragraph above via the carboxylic acid chloride with 2 mols of the aromatic monoamines listed in column III. The pigments obtained yielded orange tints possessing excellent properties of fastness in polyvinyl chloride film.

32.6 parts of 3-nitro-4-aminobenzoic acid-(2'15 -dichloro)-anilide were suspended in 300 parts of glacial acetic acid; 30 parts of 30% hydrochloric acid were added and diazotizatioin carried out at to 5 C. with 29 parts of 4 N sodium nitrite solution. After 30 minutes, the batch was diluted with 400 parts of ice-water, filtered, and the clear diazo solution run into a solution of 51 parts of 4-methoxy-3-(1-dimethylamino-methyl 2 hydroxy-3' naphthoylamino) -benzoic acid- 3 -trifiuoromethylanilide) in 2,500 parts of water and 48 parts of 2 N hydrochloric acid at to C. The batch was then bufiered to a pH value of 4.5 to 5 with a sodium acetate solution and stirred for 14 hours at 10 to C. The batch was suction-filtered, the filter residue washed with water, suspended in 250 parts of 5 N hydrochloric acid, the suspension stirred for 1 hour at room temperature, filtered and the filter residue washed with dilute hydrochloric acid and water. The pigment was treated for 2 hours in a boiling water bath with 700 parts of pyridine, filtered hot, washed with pyridine, ethanol and hot water and then dried in vacuo at 70 to 80 C. A red-orange, soft-grained powder very sparingly soluble in organic solvents was obtained. It colored polyvinyl chloride film orange tints possessing a very good fastness to migration and light when incorporated in the said film on a roller mill. The pigment so obtained had the following formula 32.6 parts of 3 nitro 4 aminobenzoic acid-(2':5'-dichloranilide) were suspended in 100 parts of hot glacial acetic acid and the suspension run into 60 parts of 30% hydrochloric acid while stirring. The batch was diazotised at 5 C. with 25 parts of a 4 N sodium nitrite solution and then filtered until clear.

Meanwhile, 50.0 parts of 4-rnethoxy-3-(2-hydroxy-3'- naphthoyl) aminobenzoic acid-3-trifluoromethylanilide were dissolved in a cold mixture of 50 parts of butanol, 200 parts of ethylene glycol monoethyl ether and parts of 30% sodium hydroxide solution. The two solutions, it necessary, after dilution with water, were led continuously into a mixing nozzle so that the diazo component and coupling component were present in equimolecular proportions in said mixing nozzle. Coupling took place immediately. The pH value in the mixing nozzle was kept between 4.5 and 6 by regulating the supply of the solutions. The temperature was kept between 35 and 40 C. and could be regulated by the addition of water to the solutions. The dyestutf suspension that formed was filtered and the filter residue washed. The filter residue was then added to a mixture of 20 parts of water, parts of ethylene glycol monoethyl ether and 100 parts of ortho-dichlorobenzene and the whole filtered at about 100 C. The filter residue was washed successively with Cellosolve, methanol and water and then dried in vacuo at 70 to 80 C. The dyestufi, which was obtained in a good yield, corresponded to product No. 29 in the table in respect of tint, purity, state of division and fastness properties.

The dyestuif was obtained in a specially fine state of division under favourable coupling conditions when an anionic or non-ionic wetting agent, for example, the sodium salt of N-benzyl-u-heptadecylbenzimidazole disulfonic acid was added to the solution of the diazo component and/or the coupling component.

Example 6 A mixture was prepared from 65 parts of stabilized 'polyvinylchloride, 35 parts of dioctylphthalate and 0.2

in which X X X represent members selected from the group consisting of hydrogen and chlorine atoms, lower alkyl, lower alkoxy, trifiuoromethyl, cyano, lower carbalkoxy and carbophenoxy groups. Z is a member selected from the group consisting of hydrogen, chlorine and lower alkoxy, Y represents a member selected from the group consisting of hydrogen and chlorine atoms, lower alkyl, lo'wer alkoxy and carboxyphenylamide groups, Y represents a member selected from the group consisting of hydrogen and chlorine atoms and lower alkoxy groups, Z and Z represent members selected from the group consisting of hydrogen, chlorine lower alkyl, lower alkoxy, phenoxy, nitro, trifiuoromethyl, cyano, carboxamido, lower carbalkoxy and carbophenoxy groups, and Z represents a member selected from the group consisting of hydrogen and chlorine atoms lower alkyl lower alkoxy groups, benzoylamino chloro benzoylamino carboxamido, lower carbalkoxy and carbophenoxy groups.

1 5 1 6 2. The dyestufi of the formula 4. The dyestuff of the formula ITIOB (J1 1}]02 C1 N-CONH N- ooNH- 11 Q 5 n N N l I 0 F3 I 01 5. The dyestuff of the formula l Cl 3. The dyestufi? of the formula 6. The dyestulf of the formula N O a C References Cited UNITED STATES PATENTS 3,174,961 3/1965 Ronco 260--203 CHARLES B. PARKER, Primary Examiner.

D. M. PAQUGA, Assistant Examiner. 

